Process for the manufacture of polyazoic dyestuffs



Patented Mar. 30, 1943 UNITED STATES PATENT. OFFICE PROCESS FOR THE MANUFACTURE OF POLYAZOIC DYESTUFFS Pierre Petitcolas, Rouen, and Robert Frdric Michel Sureau, Mont St. Aignan, France; Vested in the Alien Property Custodian N 0 Drawing. Application September 9, 1938, Se-

rial No. 229,220. In France September 14,

1 Claim.

It has been found, according to the present invention, that highly valuable dye-stuffs are obtained:

1. By coupling a diazoic' derivative of an aromatic amine or of an amine behaving, when diazotizing, as an aromatic amine and containing no group capable of conferring solubility in Water with a heterocyclic amine of the form where X represents either ECH or ECHal or EN and Z represents either H or an alkyl group or an aryl group or an aralkyl group or a cycloalkyl group, and

2. By coupling in substance or on the fibre the diazoic derivative of the amino-azoic body which has been thus obtained with a coupling component having a substantive character and by eventually treating, in substance or on the fibre, the

I chloro-indazol, the 6-amino-benz-triazol, of the formula tioned heterocyclic amines form bases which do not diazotize generally in the presence of a dipolyazoic dye-stuff thus obtained by means of metallizing agents.

The primary amines which can be used as first components according to the present process y be substituted by groups such as:

C2Hs

CH3, Hal, 0.0113, Q.C2H5, N02, S0z0. Aryl, SO2-N C 211:, SO2C2H5, NH.Acyl, CO.Ary1, and the like,

CCOH, and the like; furthermore, these amines may be of the benzenic, naphthalenic, isocyclic or heterocyclic series, provided, however, that at least one of the NHz group which they contain is diazotizable.

The heterocyclic amines which can be used as second components must be of the type above referred to, having regard to the possibility of one or more substitutions in the benzenic nucleus by such a group as CH3,Hal, O.CH3, O.C2H5 and the like, in positions such that the coupling with the diazoic of the first coupling agent is not hindered. As amines of this kind the following amines can be cited, of course by way of nonlimiting example: the G-amino-indazol of the formula:

the 6 amino-methyl-indaz ol, the '.c.-.mm'o-sluted mineral acid; it is necessary to efiectthis diazotizing with nitrosyl sulphate orin a medium of organic acid (e. g. formic or acetic acid) in the presence of a concentrated mineral acid with an alkaline nitrite. It is often possible to insulate the diazonium sulphate, which is only slightly soluble in the presence of an excess of sulphuric acid or to precipitate the fluoborate of j diazonium by an excess of a solution of fluoborate of sodium.

As coupling components having a substantive character there may be more particularly used the arylides of the orthohydroxy-carbonic acids,

but not by solubilizing groups such as SO3H,"

the arylides of the acetyl-acetic acids and the like.

The second coupling can be effected on the fibre in dyeing and in printing operations of colcuring cotton, viscose or other natural or artifi cial fibres by means of the known processes. The dye-stufis which have been produced in natura can be used for colouring lacs, varnishes, latex, paper, plastic materials, rubber, rayon silks in the mass and the like.

The said dye-stuffs ofier the interesting property of being convertible into metalliferous lacs and this conversion can also take place in natura and on the fibre.

When this transformation occurs on the fibre, the process according to our present invention is a dyeing process, according to which the fibres which have been coloured by coupling on themselves of the coupling components of substantive character, with the diazoic derivative of the above described aminoazoics, are treated by metallizing agents. It is possible, forrinstance, to proceed with the coupling in the presence of copper acetate or to copper the dye-stuffs in a slight- 1y acetic medium at boiling. Generally this treatment causes a strong bathochrome effect simultaneously With a substantial improvement of the fastness to light.

The following examples are given, of course by was of non-limiting examples:

Example 1 13.3 grams of 6-amino-indazol are dissolved in 300 ccm. of water and 10 com. of concentrated HCl. Into this solution, which is vigorously stirred, a diazoic solution is poured which has been obtained in the usual manner from '12.? grams of Qchloraniline. The coupling begins to take place in a mineral acid medium; it is rendered practically complete by adding step by step, a solution of sodium acetate until the reaction is slightly violet on Red Congo paper. The dyestuff is filtered, washed and dried.

27 grams of this dye-stuff are dissolved in 150 com. of H2804 at 66 B. Intothis solution'there is poured at ordinary temperature, and with stirring, the solution obtained by mixing:

7.5 grams of solid sodium nitrite and 35 com. of H2SO4 at 66 B.

of sodium. The crystals are filtered, washed in icy-cold water and dried in absence of light and at a moderate temperature. Since this diazoic compound is only slightly soluble, it is mixed,

of water, a considerable toning from the brownred to the dark brown is observed.

Example 3 16.8 grams of 6-amino-3-chlorindazol are dissolved in 500 ccm. of water and 10 ccm. of concentrated HCl To this solution there is added a diazoic solution prepared in the usual manner with 13.8 grams of ortho-nitraniline. The coupling is achieved by neutralizing with a solution of acetate of soda as in Example 1.

The dye-stun is filtered, washed and dried.

The diazotizing, the stabilization of the diazo and the dilution are effected as in Example 1.

' A dyeing operation which has been eiiected under the conditions of Example 2 gives a full brown passing to negro-head brown by coppering.

The following table gives the tints which have been obtained with difierent components:

'lint prior to Tim after 2-methoxy-5-nitro-aminobenzene.

First component Second component Third component (mppering coppering 2.5.-dichloro-anihne 2-nitro-4 methyl-aminobenzene. 2-nitro-4-chloro id 2.4.- dinitraniline Phenylic ether of the 5-ehloro-aminobeuzene-2-sulphonic acid. O-nitraline G-aminoindazoL.

Betanaphthylamide of the 2-3 oxynaphthoic acid.

Anilide id Betaanaplithylamide id.

p-Anisidide oi the beta-oxy-naphthoic acid. Betrin'aphthylamide id Brown yellow Redaiish-brown.

o o Dark brown 2.4.-dimethoxy-5-chlorani1ide .do

Brown-red Intensive brown Black brown Brownish black... Very dark brown.

Dark brown Khaki Reddish brown.

Dark ye'llowis h brown. Dark brown.

0. Black brown.

Dark brown. Black brown. Violet brown. Blockish brown. Black.

Brown-black.

Brownish olive.

Dark brown.

- indazol.

O-chloraniline 2.1nethyl-6-aminoindazol.

O-nitraniline fi-amino-benz-triazol.

for use, with naphthalene-trisulphonate of sodi- Lilli- .3.5 and sulphate of alumina: it can be. used for dyeing for the production of icy dye-stuffs.

Example 2 2 grams of betanaphthylamide of the betaoxynaphthoic acid are formedin a paste with 2.4 ccm. of denatured alcohol and 0.8 ccm., of a soda solution 34 B. The solution is then diluted. with 2 ccm. of cold water. A clear solution is. quickly obtained. Then 1 ccm. of 33% formaldehyde is added. After having allowed to rest for a few minutes,,there is added a litre of water to which has been previously added 5.2 ccm. of soda at 34 B. and 5 com, of .sulphoricinate of soda.

20 grams thoroughly boiled cotton thread are manipulated for an half-hour in this impregnating bath. They are then well pressed out and developed for about v15 minutes in a diazoic bath containing 15 grams. of stable diazo ofthe Nn N/' dlazotizing the coupling product obtained and coupling the diazoic derivative finally obtained with a member of the group consisting of the arylides of the orthohydroxy carbonic acids and the arylides of the acetylacetic acids.

N Hr

PIERRE PETI'TCOLAS. ROBERT FREDERIC MICHEL SUREAU. 

